Copper Tin Nickel Phosphorus Alloys With Improved Strength and Formability and Method of Making Same

ABSTRACT

A new copper-based alloy is described along with a processing method to make a strip that can be used for various automotive interconnects. The alloy process combination yields a material with high strength and electrical conductivity with excellent formability. The combination of properties result from a Cu—Sn—Ni—P alloy with optional Mg additions and thermal-mechanical processing to make an alloy with a conductivity of 40% IACS, yield strength of 80 KSI, bend formability of 1t/1t minimum, and stress relaxation of 65% at 150° C. after 1000 hours. Processing can be modified to increase formability at the expense of yield strength. Improvements to conductivity come from changes in chemistry as well as processing. The new chemistry-process optimization results in a low cost alloy of Cu—Sn—Ni—P—Mg.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Provisional Patent ApplicationSer. No. 60/979,064, filed Oct. 10, 2007, the entire disclosure of whichis incorporated herein.

BACKGROUND

This invention relates to copper alloys, and in particular tocopper-tin-nickel-phosphorus alloys with improved strength andformability.

There is a continued need for high strength copper alloys of goodformability and reasonable cost for use in electrical connectors, and inparticular for use in automotive electrical connectors. Currentconnector alloys in the low cost Cu—Sn—Ni—P family lack the combinationof properties of practical strength (77 KSI), intermediate conductivity(37% IACS), excellent formability, and decent stress relaxation (65% at150° C.). Formability in the document is measured by forming a strip byroller bending it 90° about a die of known radii. The ratio of thesmallest die radii that the strip can be formed without cracking isdivided over the strip thickness. Bends were measured both parallel (badway, BW) and perpendicular (good way, GW) to the direction of rolling.Table 1 shows currently available Cu—Sn—Ni—P alloys:

TABLE 1 Available connector alloys in the Cu—Sn—Ni—P family Stress Yieldrelaxation Alloy Strength Conductivity Bends (% SR @ (Company) (KSI) (%IACS) 90° GW 90° BW 150° C.) C19025 76 40 0.8 1   77% (Olin) C19020 6750 0.8 1.0 75% (Olin) C19500 77 40 1.5 1.5 54% (Olin) C19210 60 90 0.51.5 * (PMX) C18665 67 60 1.0 2.0 * (KME, Mitsubishi) C50715 77 35 0.50.5 * (Kobe) C50725 77 33 0.5 0.5 * (Kobe) C198 69 60 0.5 0.5 * (Kobe)C40820 80 35 S S * (Kobe)

C19025 comes close to achieving the desired properties but lacks thestrength with acceptable formability; C40820 has the strength andsuperior formability but does not have the electrical conductivity.

SUMMARY

Embodiments of the present invention provide acopper-tin-nickel-phosphorus alloy with an improved combination orproperties, and in particular improved combination of yield strength andformability. In one preferred embodiment the alloy comprises betweenabout 1% and about 2% Sn; between about 0.3% and about 1% Ni; betweenabout 0.05% and about 0.15% P, and at least one of between about 0.01%and about 0.20% Mg and about 0.02% and about 0.4% Fe, the balance beingcopper. The addition of iron can be used as a low cost substitute for ofMg if good stress relaxation is not required for the application. Morepreferably the alloy comprises between about 1.1% and about 1.8% Sn,between about 0.4% and about 0.9% Ni, between about 0.05% and about0.14% P, and between about 0.05 and about 0.15 Mg. Fe may be substitutedfor some of the Mg. Most preferably the alloy comprises, between about1.2% and about 1.5% Sn; between about 0.5% and about 0.7% Ni; betweenabout 0.09% and about 0.13% P, and between about 0.02% and about 0.06%Mg, the balance being copper. The alloy is preferably processed to havea yield strength of at least about 77 KSI, electrical conductivity of atleast about 37% IACS, and formability (90° GW/BW) of 1.0/1.0. The alloypreferably also has a stress relaxation of 65% at 150° C.

The Sn gives the alloy solid solution strengthening. Ni and Mg are addedto form precipitates of phosphorus with the added benefit of Mgincreasing strength without lowering the electrical conductivity. Themetal (Ni+Mg) to P ratio (the M/P ratio) is preferably controlled to arange of 4 to 8.5. If the ratio falls below 4 strengthening is notobtained and if is greater that 8.5 the material does not achieve 40%IACS.

In accordance with the preferred embodiment of this invention, the alloyis processed by melting and casting, hot rolling from about 850° C. toabout 1000° C. cold rolling up to about 75% annealing between about 450°C.-about 600° C., cold rolling up to about a 60% reduction followed byannealing at 425° C. to about 600° C., cold rolling to about 50% priorto the final anneal between about 400° C. and 550° C. A final cold rollreduction is given to achieve the desired thickness and mechanicalstrength prior to a thermal stress relief treatment. In anotherpreferred embodiment the processing includes a double final annealtreatment and the elimination of an upstream anneal which improvesformability and strength respectively.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a photomicrograph of the alloy in Example 1;

FIG. 2 is a graph showing the relationship between YS and M/P ratio, andillustrating the preferred M/P ratio for a Cu—Sn—Ni—P—Mg alloy;

FIG. 3 is a graphs showing the relationship between % IACS and M/Pratio, and illustrating the preferred M/P ratio of 4-8.5 ratio for aCu—Sn—Ni—P—Mg alloy;

FIG. 4A is a flow chart of a preferred embodiment of a method ofprocessing alloys in accordance with the principles of the presentinvention;

FIG. 4B is a flow chart of an alternate preferred embodiment ofprocessing alloys in accordance with the principles of this presentinvention;

FIG. 4C is a flow chart of an alternate preferred embodiment ofprocessing alloys in accordance with the principles of this presentinvention; and

FIG. 5 is a photomicrograph of an alloy (B64) after double anneal,showing a grain size of between 6-7 μm, with some areas appearing tohave not fully recrystallized grains; and

FIG. 6 is a photomicrograph of an alloy (B64) from the HR04 processafter strip anneal, showing a grain size of 4-5 μm.

DETAILED DESCRIPTION

Embodiments of the present invention provide acopper-tin-nickel-phosphorus alloy with an improved combination orproperties, and in particular improved combination of yield strength andformability. In one preferred embodiment the alloy comprises betweenabout 1% and about 2% Sn; between about 0.3% and about 1% Ni; betweenabout 0.05% and about 0.15% P, and at least one of between about 0.01%and about 0.20% Mg and about 0.02% and about 0.4% Fe, the balance beingcopper. The addition of iron can be used as a low cost substitute for ofMg if good stress relaxation is not required for the application.

More preferably the alloy comprises, between about 1.2% and about 1.5%Sn; between about 0.5% and about 0.7% Ni; between about 0.09% and about0.13% P, and between about 0.02% and about 0.06% Mg, the balance beingcopper. The alloy is preferably processed to have a yield strength of atleast about 77 KSI, electrical conductivity of at least about 37% IACS,and formability (90° GW/BW) of 1.0/1.0. The alloy preferably also has astress relaxation of 65% at 150° C.

The Sn gives the alloy solid solution strengthening. Ni and Mg are addedto form precipitates of phosphorus with the added benefit of Mgincreasing strength without lowering the electrical conductivity. TheM/P ration is preferably controlled to a range of 4 to 8.5. If the ratiofalls below 4 strengthening is not obtained and if is greater that 8.5the material does not achieve 40% IACS.

In accordance with the preferred embodiment of this invention, the alloyis processed by melting and casting, hot rolling from 850-1000° C. coldrolling up to about 75% annealing between 450-600° C., cold rollingabout 60% followed by annealing at 425-600° C., cold rolling about 50%prior to the final anneal between 400-550° C. A final cold rollreduction is given to achieve the desired thickness and mechanicalstrength prior to a thermal stress relief treatment. In anotherpreferred embodiment the processing includes a double final annealtreatment and the elimination of an upstream anneal which improvesformability and strength respectively.

EXAMPLE 1

A series of 10 pound laboratory ingots with the compositions listed inTable 2 were melted in silica crucibles and cast into steel molds whichwere after gating 4″×4″×1.75″. After soaking for 2 hours at 900° C. theywere hot rolled in three passes to 1.1″ (1.6″/1.35/1.1″), reheated at900° C. for 10 minutes, and further reduced by hot rolling in threepasses to 0.50″ (0.9″/0.7″/0.5″), followed by a water quench. Aftertrimming and milling to remove the surface oxide, the alloys were coldrolled to 0.120″ and annealed at 570° C. for 2 hours. The alloys werecleaned and cold rolled to 0.048″ and annealed at 525° C. for 2 hours.The alloys were cold rolled to 0.030″ and annealed at 500° C. for 2hours. The final cold roll was 60% to 0.012″ and a stress relief heattreatment was performed at 250° C. for 2 hours.

TABLE 2 Alloys and properties from Example 1 ALLOY % Sn % Ni % P YS* EL% IACS % 90GW 90BW Ni/P K242 0.92 0.26 0.008 65.3 8.29 51.3 nm nm 32.50K243 1.33 0.26 0.014 68.65 9.54 42.6 nm nm 18.57 K244 0.9 0.27 0.1270.85 10.46 38.4 1.33 1.5  2.25 K245 1.27 0.28 0.11 74.65 11.06 34.6 nmnm 2.55 K246 0.9 0.69 0.01 67.65 7.5 44 nm nm 69.00 K247 1.33 0.7 0.00570.2 8.2 39.7 1.67 2.33 140.00 K248 0.91 0.71 0.1 75 9.455 46.5 1.322.25 7.10 K249 1.25 0.7 0.091 79.2 10.05 40.8 1.33 2.5  7.69 K250 1.060.48 0.052 74.1 9.515 43.6 1.33 2.17 9.23 *for this Table and throughoutthis document YS means Yield Strength and is given in units of KSIFrom the data in Example 2, it was determined that the Ni level ispreferably at least 0.5 and the best overall alloys had a Ni/P ratio of7-9. All the bends were poor due to the presence of contamination ofsulfur forming long stringers as shown in FIG. 1.

EXAMPLE 2

A series of 10 pound laboratory ingots with the compositions listed inTable 3 were melted in silica crucibles and cast into steel molds whichwere after gating 4″×4″×1.75″. After soaking for 2 hours at 900° C. theywere hot rolled in three passes to 1.1″ (1.6″/1.35/1.1″), reheated at900° C. for 10 minutes, and further reduced by hot rolling in threepasses to 0.50″ (0.9″/0.7″/0.5″), followed by a water quench. Aftertrimming and milling to remove the surface oxide, the alloys were coldrolled to 0.120″ and annealed at 570° C. for 2 hours. The alloys werecleaned and cold rolled to 0.048″ and annealed at 525° C. for 2 hours.The alloys were cold rolled to 0.024″ and annealed at 450° C. for 8hours. The final cold roll was 50% to 0.012″ and a stress relief heattreatment was performed at 250° C. for 2 hours.

TABLE 3 Alloys from Example 2. 450 C./8 HRS - Single Anneal ALLOY YS EL% % IACS 90GW 90BW Sn Ni P Fe Mg M/P K279 invalid 9.41 51.2 1.00 1.171.07 0.41 0.048 0 0 8.54 K280 71.4 8.08 51 0.99 0.99 0.95 0.45 0.054 0 08.33 K281 72 11.84 50.4 1.17 1.33 0.98 0.53 0.063 0 0 8.41 K282 71.411.81 49.4 1.17 1.33 1.03 0.62 0.063 0 0 9.84 K283 71 10.68 47.9 1.171.17 0.99 0.71 0.048 0 0 14.79 K284 70.7 11.66 51.9 1.17 1.17 0.9 0.540.072 0 0 7.50 K285 73.5 10.33 48.9 1.17 1.00 1.11 0.54 0.067 0 0 8.06K286 73.9 7.31 50.4 1.16 0.99 0.96 0.53 0.095 0 0.038 5.98 K287 75.510.75 49.8 0.99 0.99 1.06 0.56 0.12 0 0.049 5.08 K288 74.1 10.7 50.21.17 1.00 0.99 0.53 0.096 0 0.058 6.13 K289 69.3 8.61 54.9 1.34 1.34 1 00.032 0 0.058 1.81 K290 71.7 9.93 52.8 1.15 1.15 1 0 0.045 0 0.14 3.11K291 74.4 10.88 50.5 1.16 1.32 1.1 0 0.095 0.38 0 4.00 K292 74.1 10.0651.5 1.00 1.00 1.05 0 0.105 0.17 0.06 2.19 K293 76.8 10.9 42.2 0.99 1.321.55 0.72 0.092 0 0 7.83 K294 80 10.62 38.4 0.99 1.16 1.79 1 0.098 0 010.20In general the strengths are low with the exception of alloys K293 andK294. Both these alloys contained more Sn than any of the others byabout 0.5% correlating higher Sn levels to higher strength. Thestrengths of K286, K287 and K288 indicate the benefit of Mg as opposedto alloys of very close composition but without Mg, K282 and K284. It isnotable that there is no drop in conductivity (the % IACS) accompanyingthe increase in yield strength. There was an increase in strength withthe addition of iron to K291 and Mg in K289 both without Ni. Theconductivity for the iron containing alloy is lower than the Mgcontaining alloy by about 4% IACS. Both of these alloys are almostperfectly balanced; Mg/P ratio is 1.81 for K289 close to the ideal of1.2 and the Fe/P ratio for K291 is 4.00 which is also close to the idealof 3.6. Iron is a more effective strengthener but leads to lowerconductivity.

EXAMPLE 3

A series of 10 pound laboratory ingots with the compositions listed inTable 4 were melted in silica crucibles and cast into steel molds whichwere after gating 4″×4″×1.75″. After soaking for 2 hours at 900° C. theywere hot rolled in three passes to 1.1″ (1.6″/1.35/1.1″), reheated at900° C. for 10 minutes, and further reduced by hot rolling in threepasses to 0.50″ (0.9″/0.7″/0.5″), followed by a water quench. Aftertrimming and milling to remove the surface oxide, the alloys were coldrolled to 0.120″ and annealed at 570° C. for 2 hours. The alloys werecleaned and cold rolled to 0.048″ and annealed at 525° C. for 2 hours.The alloys were cold rolled to 0.024″ and annealed at 450° C. for 4hours only for the single anneal condition and for 450° C. for 4 hoursplus 375° C. for another 4 hours constituting the double annealcondition. The final cold roll was 50% to 0.012″ and a stress reliefheat treatment was performed at 250° C. for 2 hours for both conditions.

TABLE 4 Alloys from example 3 including both annealing conditions. ALLOYSN NI P FE MG ZN YS EL % IACS % 90GW 90BW Single Anneal 450 C./4 hrsK310 1.54 0.51 0.042 0 0 0 74.9 13.36 38.5 0.85 1.69 K311 1.57 0.470.054 0 0 0.73 77.4 12.83 36.9 1.00 1.67 K312 1.64 0.53 0.167 0.41 0 082.2 11 37.2 0.83 1.00 K313 2.17 0.5 0.163 0.17 0 0 86.6 9.29 33.6 0.671.50 K314 1.58 0.500 0.136 0 0.052 0 81.4 13.72 38.1 0.83 1.00 K315 2.10.52 0.138 0 0.053 0 85 14.41 34 0.33 1.30 K316 1.57 0.52 0.13 0 0.049 082 11.09 39 0.66 0.82 K317 2.03 0.53 0.13 0 0.043 0 85.2 11.4 33.4 0.171.19 K318 1.59 0.5 0.073 0 0.059 0 78.4 10.42 38.5 0.83 1.16 K319 0.560.98 0.007 0 0 0 62 9.23 46.5 1.51 1.34 K320 0.93 0.98 0.025 0 0 0 68.56.34 40.8 1.03 1.03 K326 1.57 0.67 0.086 0 0 0 77.7 13.6 38.3 0.84 1.01K327 1.54 0.69 0.127 0 0.032 0 79.1 11.49 38.8 0.84 1.01 Double anneal450 C./4 hrs + 375 C/4 hrs K310 1.54 0.51 0.042 0 0 0 75 13.01 38.5 0.502.33 K311 1.57 0.47 0.054 0 0 0.73 77.3 12.7 37.1 0.33 1.64 K312 1.640.53 0.167 0.41 0 0 82.5 11.29 37.6 0.25 0.49 K313 2.17 0.5 0.163 0.17 00 87.4 13.03 34.1 0.17 0.66 K314 1.58 0.500 0.136 0 0.052 0 81.8 12.9240 0.33 0.83 K315 2.1 0.52 0.138 0 0.053 0 85 13.52 34.2 0.66 0.82 K3161.57 0.52 0.13 0 0.049 0 81.3 14.23 39.5 0.50 0.83 K317 2.03 0.53 0.13 00.043 0 85.3 11.63 33.8 0.17 0.50 K318 1.59 0.5 0.073 0 0.059 0 78.311.86 38.7 0.34 0.50 K319 0.56 0.98 0.007 0 0 0 62.6 4.91 46.6 0.10 1.34K320 0.93 0.98 0.025 0 0 0 68.9 6.87 41.5 0.33 0.33 K326 1.57 0.67 0.0860 0 0 78.2 12.16 38.5 0.10 0.82 K327 1.54 0.69 0.127 0 0.032 0 79.312.37 39.7 0.66 0.99Higher Sn levels helped the strength levels considerably but at lowerconductivities. Compare alloys K320 and K319; 7 KSI difference in YS and3% IACS in conductivity. The trend holds for those alloys with iron(K312 and K313) and those with magnesium (K 314 and K315) although theimpact on strength is less than those without any other addition. Therewas no overall advantage of zinc K311 in contrast to K310; strength isincreased but with lower conductivity. The double anneal showed anincrease in formability (i.e., a decrease in the 90° bend radii that canbe achieved). Slight increases in the conductivities are also noted.

EXAMPLE 4

A series of 10 pound laboratory ingots with the compositions listed inTable 4 were melted in silica crucibles and cast into steel molds whichwere after gating 4″×4″×1.75″. After soaking for 2 hours at 90° C. theywere hot rolled in three passes to 1.1″ (1.6″/1.35/1.1″), reheated at900° C. for 10 minutes, and further reduced by hot rolling in threepasses to 0.50″ (0.9″/0.7″/0.5″), followed by a water quench. Aftertrimming and milling to remove the surface oxide, the alloys were coldrolled to 0.120″ and annealed at 570° C. for 2 hours. The alloys werecleaned and cold rolled to 0.048″ and annealed at 525° C. for 2 hours.The alloys were cold rolled to 0.024″ and annealed at 450° C. for 4hours only plus 375° C. for another 4 hours. The final cold roll was 50%to 0.012″ and a stress relief heat treatment was performed at 250° C.for 2 hours.

TABLE 5 Data from example 4 ALLOY YS EL % IACS % 90GW 90BW SN NI P FE MGM/P K335 71.5 11.41 42.4 0.26 0.26 1.13 0.52 0.086 0 0 6.05 K336 71.29.93 41.4 0.34 0.17 1.28 0.69 0.053 0 0 13.02 K337 72.5 12.08 41.7 0.080.17 1.46 0.51 0.075 0 0 6.80 K338 76.3 12.78 38.2 0.08 0.25 1.38 0.530.099 0.37 0 9.09 K339 78.9 11.99 36.6 0.08 0.67 1.7 0.53 0.105 0.33 08.19 K340 73.6 12.66 41.4 0.17 0.50 1.45 0.52 0.079 0 0 6.58 K341 73.511.79 39.1 0.17 0.34 1.47 0.69 0.064 0 0 10.78 K342 73.5 11.76 41.7 0.250.16 1.43 0.53 0.067 0 0 7.91 K343 75.2 12.77 38.4 0.08 0.33 1.71 0.530.08 0 0 6.63 K344 71.9 10.51 38 0.67 0.67 1.67 0.52 0.033 0 0 15.76K345 74.8 11.84 38.6 0.08 0.17 1.61 0.69 0.076 0 0 9.08 K346 74.8 10.0238.4 0.08 0.08 1.35 0.32 0.105 0.4 0 6.90 K347 76.5 10.58 41.4 0.08 0.171.38 0.3 0.143 0.23 0 3.70 K348 75.4 12.48 32.8 2.00 3.00 1.71 0.320.139 0 0 2.40 K349 70.5 12.53 41.5 0.50 0.50 1.35 0.53 0.035 0 0 15.14K350 76.3 13.37 38.1 0.17 0.25 1.62 0.7 0.081 0 0.031 9.00 K351 76.310.72 40.6 0.08 0.33 1.35 0.69 0.092 0 0.049 8.00 K352 75.8 12.55 410.17 0.17 1.37 0.54 0.129 0 0.021 4.30 K355 78.7 13.83 37.1 0.25 0.501.74 0.32 0.145 0.21 0 3.66 K356 75.6 11.99 41.5 0.67 0.67 1.42 0.540.09 0 0.041 7.00 K361 78.7 15.11 34.2 0.34 0.50 1.7 0.33 0.151 0.043 02.47Thirteen of the twenty-two alloys in this group had yield strengths of75 KSI or above. Six contained iron (K338, K339, K345, K346, K355 andK361) none of which made electrical conductivity of 40% IACS, althoughK338 is the closest at 38% IACS. Four contained Mg (K350, K351, K352 andK356) and 3 of these 4 exceeded 40% IACS. Note that K350 which did notachieve 40% IACS had a metal to phosphorus ratio of 9, greater that therecommended 8.5. Three of the alloys with yield strengths of 75 ksi orgreater contained neither iron nor Mg (K343, K345, and K348), but noneof these alloys had conductivities of 40% IACS.

EXAMPLE 5

All the data for Mg containing alloys and Mg-free alloys are combined inTables 6 and 7. These data are from example 2, (Table 3 alloys whichwere double annealed and included in Tables 6 and 7), Example 3 (Table4), and Example 4 (Table 5), and include data from Example 3. Theprocess used for all the alloys is identical to the process used in thefinal double anneal of 4 (or 8 hours; see note) at 450° C.+4 hours at375° C.

TABLE 6 Grouped data from Examples with Mg, all double annealed

Note: Alloys in highlighted in light gray had a slightly different finaldouble anneal 450° C. for 8 hours + 4 hours at 375° C.

TABLE 7 Grouped data from all Examples without Mg, all double annealed

*Alloys K 319 and K320 are similar to C19020 and C19025, but with lowerP. Alloys in highlighted in light gray had a slightly different finaldouble anneal 450° C. for 8 hours + 4 hours at 375° C.

Overall the YS in Table 6 with Mg are higher than those in Table 7without Mg. Only a few Mg-free alloys reach a minimum YS of 75 KSI:K293, K294, K310, K326, K343, K345, and K348, with correspondingelectrical conductivities of: 42.2, 38.5, 38.5, 38.5, 38.4, 38.6 and32.8% IACS respectively. Note with the exception of K293 none of thealloys achieve 40% IACS. Alloys K293, K294 and K326 all have propertiesof YS and conductivities close to C19025 but have better bends. Incontrast the Mg alloys in Table 6 all have YS of at least 75 KSI withthe exception of K289 and K290 (which had no Ni and an M/P ratio below4). The electrical conductivities of all the alloys are at or above 40%IACS except for K318 (38.7% IACS) with an M/P of 7.66 and K350 (38.1%IACS) with an M/P ratio of 9.02. As the metal to phosphorus ratioincreases the conductivity decreases and the combination of desirableproperties becomes more difficult to reach. The addition of Mg enablesthe combination of yield strength over 75 KSI and conductivity of atleast 40% IACS achievable when employing appropriate processing andmaintaining an M/P ratio between 4 and 8.5. FIGS. 2 and 3 illustrate therelationships between the ratios and YS and % IACS respectively. Thevertical lines in FIG. 2 show the preferred M/P ratio of 4-8.5.

EXAMPLE 7

A series of 10 pound laboratory ingots with the compositions listed inTable 8 were melted in silica crucibles and cast into steel molds whichwere after gating 4″×4″×1.75″. After soaking for 2 hours at 900° C. theywere hot rolled in three passes to 1.1″ (1.6″/1.35/1.1″), reheated at900° C. for 10 minutes, and further reduced by hot rolling in threepasses to 0.50″ (0.9″/0.7″/0.5″), followed by a water quench. Aftertrimming and milling to remove the surface oxide, the alloys were coldrolled to 0.080″ and annealed at 550° C. for 2 hours. The alloys werecleaned and cold rolled to 0.036″ and annealed at 450° C. for 4 hoursonly plus 375° C. for another 4 hours. The final cold roll was 60% to0.012″ and a stress relief heat treatment was performed at 250° C. for 2hours.

TABLE 8 Data from Example 7 ALLOY TS YS EL % IACS % 90GW 90BW SN NI P MGMetal/P K340 84.4 81.2 9.72 41.2 0.2 1.0 1.45 0.52 0.079 0 6.58 K34184.1 80.9 12.16 39.2 0.3 1.2 1.47 0.69 0.064 0 10.78 K350 87.6 84.414.24 37.3 0.1 0.8 1.62 0.7 0.081 0.031 9.02 K352 87.6 83.8 11.58 41 0.21.3 1.37 0.54 0.129 0.021 4.35Increased cold work improved strength for all alloys. However, the Mgcontaining alloy with an M/P ratio below 9 (K352) was the only one toimprove YS white maintaining or improving conductivity.

EXAMPLE 8

A series of 10 pound laboratory ingots with the compositions listed inTable 3 were melted in silica crucibles and cast into steel molds whichwere after gating 4″×4″×1.75″. After soaking for 2 hours at 900° C. theywere hot rolled in three passes to 1.1″ (1.6″/1.35/1.1″), reheated at900° C. for 10 minutes, and further reduced by hot rolling in threepasses to 0.50″ (0.9″/0.7″/0.5″), followed by a water quench. Aftertrimming and milling to remove the surface oxide, the alloys were coldrolled to 0.120″ and annealed at 570° C. for 2 hours. The alloys werecleaned and cold rolled to 0.048″ and annealed at 525° C. for 2 hours.The alloys were cold rolled to 0.024″ and annealed at 450° C. for 4hours minimum. The final cold roll was 50% to 0.012″ and a stress reliefheat treatment was performed at 250° C. for 2 hours. The samples weresubjected to stress relaxation testing at 150° C. for 1000 hrs. Theresults are given in Table 9 below:

TABLE 9 Data from Example 8 % Stress Alloy Composition Remaining K291Cu—1.1Sn—0.38Fe—0.095P 56.6 K312 Cu—1.64Sn—0.53Ni—0.41Fe—0.167P 58.7K314 Cu—1.58Sn—0.50Ni—0.052Mg—0.136P 66.8Alloys K291 and K312 with iron did not maintain 60% of the initialstress. The results are similar between the two despite the presence ofNi in K312. K314 with Ni and Mg combination maintained more than 65% ofthe initial stress.

EXAMPLE 9

A set of Mg and Mg-free alloys were processed using the indicatedschedules. Tables 10 and 11 summarize the results. Both sets of alloysachieved yield strengths over 80 KSI. The Mg-containing alloys, allexceeded the target conductivity of 38% IACS, whereas the Mg-freealloys, with the exception of K412, did not. In addition, theformability of the Mg-containing alloys was generally better.

TABLE 10 Summary of Results for Mg-Containing alloys ALLOY YS EL % %IACS 90GW 90BW Sn Ni P Mg Metal/P K373 80.3 11.69 43.7 0.50 1.01 1.130.5 0.077 0.016 6.70 K374 81 11.17 42.9 0.17 1.00 1.17 0.71 0.085 0.018.47 K375 83.3 13.17 38.8 0.08 1.33 1.54 0.7 0.091 0.014 7.85 K376 8311.14 39.1 0.17 1.00 1.52 0.52 0.104 0.017 5.16 K351 83.8 10.45 40.90.17 0.83 1.35 0.69 0.092 0.049 8.03 K356 82.1 10.57 42.4 0.08 1.01 1.420.54 0.09 0.041 6.46 K394 87.6 10.13 39.9 0.08 0.83 1.41 0.51 0.16 0.063.56 K395 84.1 9.81 43.3 0.08 0.83 1.27 0.5 0.06 0.055 9.25 K399 84.712.78 39.9 0.25 2.33 1.42 0.5 0.094 0.042 5.77 K400 84.9 10 39.4 0.081.18 1.61 0.51 0.159 0.044 3.48 K401 82.7 9.53 38.4 0.08 0.67 1.54 0.710.074 0.02 9.86 K402 87.2 11.09 39.4 0.08 0.83 1.51 0.71 0.11 0.028 6.71YS is in KSI Process Details: HRP + CR to 0.060 gage + 500° C./8 hrs +CR 50% to 0.030 gage + 450° C./4 hrs + 375° C./4 hrs + CR 60% to 0.012gage + 250° C./2 hrs

TABLE 11 Summary of Results for the Mg-free alloys IACS 90 Alloy YS EL %% GW 90BW Sn Ni P Ni/P K378 86.3 12.58 37.8 0.98 1.48 1.5 0.99 0.12 8.25K412 83.1 12.88 39.5 0.99 1.32 1.6 0.49 0.05 9.80 K413 83.4 12.44 35.90.83 1.17 1.65 1.1 0.048 22.92 K414 83.3 10.4 35.8 0.85 1.69 1.89 0.480.03 16.00 K415 85.7 12.36 37.1 0.08 1.67 1.9 0.48 0.08 6.00 K416 86.17.35 32.6 0.25 1.51 1.93 1.1 0.044 25.00 YS is in KSI Process Details:HRP + CR to 0.060 gage + 475° C./16 hrs + CR 50% to 0.030 gage + 450°C./4 hrs + 375° C./4 hrs + CR 60% to 0.012 gage + 250° C./2 hrs

EXAMPLE 10

Plant processing was conducted on six alloys whose nominal compositionsare set forth in Table 12. The processes are detailed in Table 13, whereProcess 1 is a laboratory process for comparison purposes, and Processes2, 3, and 4 are plant processes.

TABLE 12 Chemistry of Plant-Processed Bars Alloy Sn Ni P Mg 1 1.64 0.880.074 0 2 1.7 0.65 0.1 0 3 1.39 0.65 0.1 0.035 4 1.42 0.68 0.11 0.038 51.66 1 0.1 0 6 0.91 0.98 0.056 0

The chemistry given in the Table 12 is the analyzed chemistry for thecast bars. Alloy 6 lies within the CDA range for C19025 and is presentas a comparative example. All alloys were processed the same way: Theywere all hot rolled from 900° C., coil milled and then cold rolled to0.125 or 0.100 gauge.

TABLE 13 Definition of Processes for Example 10 Process 1 Process 2Process 3 Process 4 HR HR + CR→0.100 HR + CR→0.125 HR + CR→0.125CR→0.060 CR→0.060 Anneal Anneal 500° C. Anneal 520° C. Anneal 520° C.500° C./8 hr to adequately to adequately to adequately recrystalizerecrystalize recrystalize CR→0.030 CR→0.0295 CR→0.0295 CR→0.0513 450°C./4 h + 450° C./6 h + 570° C. 580° C. 375° C./4 h 25° C./h slow cool to375° C./5.5 h CR→0.012 CR→0.0118 CR→0.0118 CR→0.0118 250° C./2 h 400° C.400° C. 400° C.The resulting properties at final gage are shown in Table 14. Alloy 6processed using Processes 3 and 4 possessed the expected properties forthis alloy, having higher yield strength and poorer bends for Process 4versus Process 3. Alloy 5 had a lower yield strength (YS) and poorer badway bends when processed according to Process 2 in contrast to theProcess 3 metal. Alloy 3 had comparable yield strength and conductivityfor both the Process 2 and Process 3 processing but metal processedaccording to Process 3 had better bad way bends.

TABLE 14 Results from the Plant Trial as Compared to the LaboratoryProcessed Metal Alloy Process 2 Process 3 or 4* Process 1 Results YSIACS GW BW YS IACS GW BW YS IACS GW BW Alloy 6 77.2 41.5 0.17 1.36 — — —— — — — — — — — — 75.3 41.6 0.09 0.88 — — — — — — — — 79*  41.4* 0.18*1.67* — — — — Alloy 5 82.6 35.4 0.08 1.27 85.3 34.8 0.08 1.03 — — — —Alloy 1 80.5 35.4 0.08 1.11 — — — — 81.0 36.6 0.08 0.50 Alloy 2 81 37.40.08 0.94 — — — — — — — — Alloy 3 81.6 40.7 0.08 1.10 81.8 39.7 0.080.68 — — — — Alloy 4 81.5 40.5 0.08 1.28 82.7 39.6 0.08 0.59 81.6 40.90.17 0.33 *These results are from process 4.Processes 3 and 4 generally gave the best results. The results forProcesses 1 and 2 on alloys 1 and 4 show slightly different results ifthe process is conducted in the plant (Process 2) rather than in the lab(Process 1) may have caused grain growth. Table 15 shows that the doubleanneal process (Process 2) gives good bends when simulated in the lab.

TABLE 15 Additional results for Alloy 4 TS (KSI) YS (KSI) Elong. (%) %IACS GW90 BW90 86.5 83.7 10.27 40.4 0.09 0.52

Plant processed alloys were subjected to stress relaxation testing at150° C. Results for the transverse direction only are shown below inTable 16. All alloys except for alloy 2 had at least 65% stressremaining after 1000 h at 150° C.

TABLE 16 Stress Relaxation Data from the Plant Trial Process 2 Process 3or 4* Results SR % 500 h SR % 1000 h SR % 500 h SR % 1000 h Alloy 6 70.066.5 74.8 71.6 79.4 75.8 Alloy 5 72.5 68.7 76.2 72.1 Alloy 1 74.4 67.8 —— Alloy 2 69.0 64.3 — — Alloy 3 74.2 66.6 75.3 69.2 Alloy 4 71.4 66.573.8 68.2

1. A copper base alloy comprising between about 1% and about 2% Sn;between about 0.3% and about 1% Ni; between about 0.05% and about 0.15%P, and at least one of up to about 0.20% Mg and between about 0.1 andabout 0.4% Fe, the balance being copper.
 2. The copper base alloyaccording to claim 1 containing Mg but no Fe.
 3. The copper base alloyaccording to claim 1 containing Fe but no Mg.
 4. The copper base alloyaccording to claim 1 containing both Mg and Fe.
 5. The copper base alloyaccording to claim 1 containing up to about 0.06% Mg.
 6. The copper basealloy according to claim 1 processed to have a yield strength of atleast about 77 ksi, while maintaining bend formability (90° GW/BW) of1.0/1.0.
 7. The copper base alloy according to claim 6 wherein the alloyis processes to have a conductivity of at least about 37% IACS.
 8. Thecopper base alloy according to claim 6 wherein the alloy is processed tohave a conductivity of at least about 40% IACS
 9. The copper base alloyaccording to claim 1 wherein the Ni:P ratio is less than about
 9. 10.The copper alloy according to claim 1 wherein the (Ni+Mg):P ratio isbetween about 4 and about 8.5.
 11. The copper base alloy according toclaim 1 wherein the Sn is between about 1.2% and about 1.5%, the Ni isbetween about 0.5% and 0.7%, and the P is between about 0.09% and about0.13%.
 12. The copper base alloy according to claim 11 wherein the Ni:Pratio is less than about
 9. 13. The copper alloy according to claim 11wherein the (Ni+Mg):P ratio is between about 4 and about 8.5.
 14. Thecopper base alloy according to claim 11 processed to have a yieldstrength of at least about 77 ksi, while maintaining bend formability(90° GW/BW) of 1.0/1.0.
 15. The copper base alloy according to claim 14wherein the alloy is process to have a conductivity of at least about37% IACS.
 16. The copper base alloy according to claim 14 wherein thealloy is process to have a conductivity of at least about 40% IACS. 17.A copper base alloy comprising between about 1.2% and about 1.5% Sn;between about 0.5% and about 0.7% Ni; between about 0.09% and about0.13% P, and at least one of up to about 0.20% Mg and between about 0.1and about 0.4% Fe, the balance being copper, the alloy processed to havea yield strength of at least about 77 ksi, and an electricalconductivity of at least about 37% IACS.
 18. The copper base alloyaccording to claim 17 wherein the alloy is processed to have aconductivity of at least about 40% IACS.
 19. The copper base alloyaccording to claim 17 processed to have a bend formability (90° GW/BW)of 1.0/1.0.
 20. The copper alloy according to claim 11 wherein the(Ni+Mg):P ratio is between about 4 and about 8.5.
 21. A method ofprocessing a copper base alloy comprising between about 1% and about 2%Sn; between about 0.03% and about 1% Ni; between about 0.05% and about0.15% P, and at least one of up to about 0.20% Mg and between about 0.1and about 0.4% Fe, the method comprising: casting the alloy; hot rollingthe alloy at about 850 to about 1000° C.; subjecting the alloy to atleast one cold rolling and annealing to substantially recrystalize thealloy; cold rolling the alloy to the desired thickness and mechanicalstrength; and subjecting the alloy to a thermal stress relief treatment,to provide an alloy with a yield strength of at least about 77 ksi andan electrical conductivity of at least about 37% IACS.
 22. The methodaccording to claim 21 wherein there are at least three cold rollings andannealings.
 23. The method according to claim 22 wherein the at leastthree cold rollings and annealings comprise: a first cold rolling up toabout a 75% reduction followed by annealing between about 450 and about600° C. for 1 to 48 hours; a second cold rolling up to about a 60%reduction followed by annealing at about 425 and about 600° C. for 1 to48 hours; and a third cold rolling up to about a 50% reduction followedby an annealing at between about 400 and about 550° C. for 1 to 48hours.
 24. The method according to claim 22 wherein one of theannealings comprises a step anneal.
 25. The method according to claim 24wherein the step anneal comprises a first anneal at between about 400and about 500° C. followed by a second anneal at between about 300 andabout 400° C.